Highly-fluorinated monomers, polymers and copolymers



3,280,083 HIGHLY-FLUORINATED MONOMERS, POLYMERS AND COPOLYMERS AnthonyJ. Butler, George A. Grindahl, and Ogden R. Pierce, Midland, Mich.,assignors to Dow Corning Corporation, Midland, Mich., a corporation ofMichigan No Drawing. Filed Feb. 7, 1964, Ser. No. 343,214 4 Claims. (Cl.260-821) This invention relates to new, highly-fluorinated polymers andcopolymers, and new monomers from which they are made.

The polymers and copolymers of this invention exhibit fine solvent andheat resistance, and show promise as new additions to the field ofmoldings and coatings.

The polymeric compositions of this invention can be described as apolymer comprising units, where each R can be hydrogen, fluorine, or aperfiuoroalkyl radical, no more than one R group being hydrogen, and nis an integer of 2 to 3.

Other copolymeric units can also be present in the compositions of thisinvention, such as those which are selected from the group consisting ofunits, where X is selected from the group consisting of fluorine andhydrogen, at least one X being hydrogen, V is selected from the groupconsisting of the trifluoromethyl radical and fluorine, and R is asdefined above, the number of Xs that are hydrogen exceeding the numberof Rs that are hydrogen;

units, where X is as defined above, and Q is selected from the groupconsisting of hydrogen, fluorine, and methyl, at least one of the abovesymbols being H; CZ CX=CXCZ units, where Z is selected from the groupconsisting of the trifluor-omethyl radical, fluorine, and hydrogen, andX is selected from the group consisting of fluorine and hydrogen; and

units, where m is an integer of 1 through 2, Y is selected from thegroup consisting of methyl radicals and hydrogen, and Z is as definedabove.

R can consist of fluorine, hydrogen, or any perfluoroalkyl radical suchas trifluoromethyl, pentafluoroethyl, perfluoroisobutyl, perfluorooctyl,etc. i

The polymers and copolymers of this invention can be made bypolymerizing (1) the monomer of this invention (a new composition ofmatter),

with itself, or with other conjugated olefins such as (2):

I United States Patent Patented Oct. 18, 1966 "ice where the symbols areas defined above.

The copolymers of this invention can be made with more than one speciesof the monomer of this invention.

It is preferred for the copolymers of this invention to contain from 5to mol percent of the unit or units formed from ingredient (1) and from95 to 5 mol percent of the unit or units formed from ingredient 2.

The polymerization reaction may be conveniently eflected by using aredox initiation, as in Example 3.

The monomer of this invention can be made by dehydrofluorinatingonnormnornonorhom by means of anhydrous lithium hydroxide, with mineraloil as a medium. A reflux for several hours is usually required.

Compound (3) can be prepared by dehydration in the following manner:

Compound (4) can be prepared in the following manner:

0 30 20 CR2(CR1)..CF=CF ditertiary butyl peroxide; heat; in a bomb 02(OR2)nO FYI 3 FOHGH;

Example 1 240 g. of

0 F 0 F20 FQCFHO FCH=CH1 36 g. of anhydrous lithium hydroxide, 200 ml.of mineral oil, and a trace of hydroquinone as a polymerizationinhibitor were placed in a 500 ml. flask and refluxed with vigorousstirring for 16 hours.

The volatiles were then stripped to obtain 171 g. of

A trace of (EFgCFgCF=CFCFCH=OHg was also recovered.

Example 2 To an 8 inch polymer tube was added 0.2 g. of K S O and 0.6 g.of potassium perfiuorooctoate. Following an N purge of the tube, g. of

was slowly added, with intermittent N purges. Finally, 40 g. of waterwere added. The tube was then evacuated and placed under an N atmosphereat atmospheric pressure and sealed. The tube was agitated in warm (45C.) water for 20 hours.

The product was coagulated, washed with water, and dried.

18 g. of 1a homopolymer of the above vinylperfluorocyclopentene wasrecovered. It was a white powder which softens to a viscous, flowingmaterial at 250 C.

The polymer was placed for 18 hours at 250 C. in a forced air oven. Itsweight loss was 12.7%.

Infrared spectroscopy showed that the polymerization had occurred onlyon the vinyl groups leaving the unsaturated rings as pendant groups.

The homopolymer is insoluble in common, organic solvents.

Example 3 Copolymers of and CH =CHCN were made by the followingprocedure. The following were placed in a polymer tube and agitated in a50 C. water bath for 20 hours:

Both batches yielded copolymers that were then coagulated, Washed, anddried. They were both white thermoplastic powders that were insoluble incarbon tetrachloride, benzene, tetrachloroethylene, acetone, andboiling, concentrated KOH solution. The copolymers were composed ofunits of the formulae Example 4 and A copolymer of and CH =CHCH=CH wasprepared in the following manner:

To a polymer tube was added 15 g. of

ExampleS A copolymer of -CH=CH5 and CF CFCH=CH was prepared in thefollowing manner:

The following was placed in a stainless steel bomb: 10.8 g. of

CH=CH3 14.2 g. of CF :CFCH=CH 0.17 g. of K S O 0.0085 g. of FeSO -7H O,0.085 g. NaHSO 0.85 g. of C F COOK, and 60 m1. of water buffered to pH10.

The bomb was agitated on an Amnico rocker at 50 C. for 18 hours.

The product Was precipitated with methanol and saturated salt water,:and dried at C.

23 g. of a tough, elastomeric copolymer was recovered, consistingessentially of & HOH:

units and C H-CHP F: units.

Example 6 When g. of the following compounds are mixed with 36 g. ofanhydrous lithium hydroxide, 200 ml. of mineral oil, and trace ofhydroquinone as -a polymerization inhibitor, and the mixture is refluxedfor 20 hours, the following products are obtained:

Reactant Product (IJFa (13F: CFzOFCFzOFHCFCH=OHg CFaCF CF2CF=COH=CH1CaF17 CF! CgFn CF;

OH CFaCF CFH CF CH=CH2 CF1( CFa) sCFH CF CH=OH a 'I CHa Example 7 Wheng. of mixtures of the followingicompounds are shaken together and warmedin the presence of g. of water, 0.25 g. of K s og, 0412 g. of N-aHS00.012 g. Of F6SO '7H O, and 0.5 of C H COOK, O0-

polymers of the following compounds are formed in the proportionsstated. The ingredients in the left hand col umn polymerize 1,2 only,forming pendant groups.

. a 6 That whichis claimed is: 11. A oopolymer consisting essentially of(a) '5 to 95 mol percent of units where each R is selected from thegroup consisting of hydrogen, fluorine, vand perfluoroalkyl Percent ofmixture and copolymer Percent of mixture and copolymer eFn =CH OF 0H;

UHF C CN CHF=CH CN CH: CH:

CH=CH 7 radicals, no more than one R group being hydrogen, and n is aninteger of 2 to 3; and (b) 95 to 5 mol percent of units selected fromthegroup consisting of (1) OXCX2 I R ARV units, Where X is selected fromthe group consisting or fluorine and hydrogen, at least one X beinghydrogen, V is selected from the group oonsisting of the trifluoromethylradical and fluorine, and R is as defined above, the number of Xs thatare hydrogen exceeding the number of Ris that are hydrogen;

-OX C Q,-

units, Where X is as defined above, and Q is selected from the groupconsisting of hydrogen, fluorine, and

methyl, at least one of the above symbols being hydrogen;

(3 -CZ OX=CXCZ Where Z is selected from the group consisting offluorine, the trifluoromethyl radical .and hydrogen, and X is as definedabove; and

011!) Where m is an integer of 1 through 2 each (--CYC'H group presentbeing separately attached to the above phenyl ring, Y is selected fromthe group consisting 8 of the methyl radical and hydrogen, and Z is asdefined above. 2. The oopolymer of claim 1 where (a) is CZ'FQC F F30F=9lH-CH1 and (b) is CII,( JHCN 3. The copolyrner of claim II where (a)is and '(b) is CH CH=CHCH 4. The c-opolymer of claim :1 Where (a) isOTHER REFERENCES Cofiman et al.: J.A.C.S., 71 (1949), pp. 490-6.

JOSEPH L. SOHOFER, Primary Examiner.

H. Wong, Assistant Examiner.

1. A COPOLYMER CONSISTING ESSENTIALLY OF (A) 5 TO 95 MOL PERCENT OF 